Quinone類化合物是一種普遍存在自然環境中的電子傳遞物質，有助於電子從還原劑上轉移至諸如四氯化碳等氯化碳氫化合物以加速其在還原態環境中的降解。在本研究中，針對五種quinone類化合物於硫環境下對四氯化碳的還原脫氯反應進行探討，結果顯示添加quinone類化合物能加速還原脫氯的反應速率達2至40倍，且反應速率的增加與使用的quinone類化合物具有相當的依存性，由快至慢依次為NQ > BQ >> AQDS > MQ ~ LQ。進一步分析各quinone化合物於硫化氫環境中的光譜變化，可推論quinone類化合物會因化學結構的不同而產生不同的活性物質以利電子的傳遞；對BQ及NQ而言，在與硫化氫共存時會因加成反應而生成反應性強的硫化quinone化合物。而AQDS則具有極低的氧化還原電位，會在硫化氫環境中生成quinone自由基型態而加速氯化有機物的還原降解反應。LQ及MQ則會在相同環境下生成還原態quinone化合物。另外，研究也發現pH值會大幅影響quinone類化合物對於還原脫氯反應的速率。有鑑於自然環境中腐植質含有許多的quinone官能基，因此本研究中亦選用兩種腐植酸探討其quinone官能基與還原脫氯反應的關聯性，在添加腐植酸的實驗中，四氯化碳的分解效率可提升1.6至2.4倍，配合光譜分析的結果，推論這兩種腐植酸皆是以還原態quinone化合物作為活性電子傳遞物質。

The dechlorination of carbon tetrachloride (CT) in homogeneous aqueous solutions containing quinone compounds as electron mediators and thiol compounds as bulk reductants was investigated. The use of thiol compounds including sodium hydrosulfide and cysteine as bulk reductant can effectively dechlorinate CT. The dechlorination of CT followed pseudo first-order kinetics and the pseudo first-order rate constant (kobs) was 0.051 d-1 with 5 mM NaHs and 0.009 d-1 with cysteine. Addition of quinone compounds including AQDS, benzoquinone (BQ), naphthoquinone (NQ), lawsone (LQ) and menadione (MQ) could significantly increase the rate and efficiency of CT dechlorination. The enhanced effect followed the order of NQ > BQ >> AQDS > MQ~LQ. A 2- to 40-fold increase in kobs relative to the solutions in the absence of quinone compounds was observed. Spectroscopic results including EPR, FTIR, UV-Vis and LC-MS showed that the selected quinone compounds can form various active electron mediators for electron transfer and can be categorized into three groups. The first group included BQ and NQ that could produce mercaptoquinone as active redox mediators. The second one included AQDS and the quinone moiety can be reduced to semiquinones. Moreover, lawsone and menadione can be reduced to hydroquinone by thiol compound to slightly enhance the dechlorination efficiency of CT. Environmental factors such as pH value, concentrations of thiol and quinone compounds can significantly influence the dechlorination efficiency and the rate of CT and exhibited positive correlations between the kobs for CT dechlorination and environmental factors. Moreover, two humic acids, Aldrich and Yang-ming mountain humic acid were shown to be reduced to hydroquinone moieties as active electron mediators by hydrosulfide ion and the kobs for CT dechlorination were 1.6 — 2.4 times higher than that without humic acid. Since humic substances contain large quinone moiety and sulfur compounds and are abundant under anaerobic conditions, results obtained in this study indicate the potentials of utilizing humic substances for effective electron mediators.

謝誌 i
中文摘要 ii
Abstract iii
Content Index v
Table Index viii
Figure Index x
Chapter 1. Introduction and motivation 1
1-1 Motivation 1
1-2 Objective 3
Chapter 2. Background and theory 6
2-1 Physicochemical properties of chlorinated hydrocarbons 6
2-2 Physicochemical properties of quinone compounds 6
2-2-1 The redox cycling property of quinone compounds 11
2-2-2 The chemistry of semiquinone 16
2-2-2-1 Determine radical by EPR 23
2-2-3 The reaction of nucleophilc molecules and quinones 26
2-3 The reductive degradation mediated by quinone compounds 28
2-3-1 Quinone moieties in humic substances 35
2-3-2 Reduction of quinone compounds 37
2-3-3 The reductive degradation of priority pollutants using quinones 38
2-3-3-1 The pH value 42
2-3-3-2 The redox potential 44
2-3-3-3 The semiquinone radical 46
2-4 Mechanism for dechlorination of chlorinated hydrocarbon by quinone compounds 46
Chapter 3. Materials and methods 51
3-1 Research design 51
3-2 Chemicals 53
3-3 Experimental procedures 53
3-3-1 Preparation of anoxic solution 53
3-3-2 Effect of bulk reductants on CT degradation 57
3-3-3 Effect of quinone compounds on CT degradation 57
3-3-4 Effect of humic acids on CT degradation 62
3-4 Analytical methods 62
3-4-1 Analysis of carbon tetrachloride and the intermediates 62
3-4-2 Production of free radicals 65
3-4-3 Characterization of the functional group change 66
3-4-3-1 Characterization using UV-visible 66
3-4-3-2 Identification of the function group by FTIR 66
3-4-3-3 Analysis of the intermediates by LC-MS 67
3-4-3-4 Charge distributions using program simulation 67
Chapter 4. Results and discussion 68
4-1 Effect of reductants on CT dechlorination without mediator 68
4-2 Effect of quinone compound on CT dechlorination 70
4-3 The spectroscopic study on the effect of quinone compounds 80
4-3-1 EPR spectra 87
4-3-2 UV-Visible spectra 93
4-3-3 FTIR spectra 102
4-3-4 LC-MS spectra 109
4-3-5 Summarization 114
4-4 The effect of environmental parameters on NaHS-quinone remediation of CT 119
4-5 The application of quinone moieties on humic acid 134
Chapter 5. Conclusions 140
References 145
Appendix A. EPR spectra 152
Appendix B. UV-Visible spectra 161
Appendix C. FTIR spectra 167
Appendix D. Humic acid spectra 171
Appendix E. Derivation of equation 2-8, 2-15 and 2-16. 175

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